Hair colouring compositions

ABSTRACT

A hair colouring composition contains an oxidative hair dye and at least one antioxidant agent selected from the group consisting of  rosmarinus officinalis, origanum vulgare, camellia sinensis, camellia oleifera, salvia officinalis, apium graveolen, thymus vulgaris, rosa canina  and  coriandrum sativum  in combination with a suitable diluent or carrier. The hair colouring compositions are gentler on the skin and hair in that they reduce the effects or the oxidising agent on the hair and skin.

The present invention relates to compositions used to colour the hairand to methods of using such compositions to treat the hair.

The term “hair colouring composition” as used herein comprises anycomposition which includes means semi-permanently or permanently tocolour, tint and/or dye the hair. Such compositions include so-calledshampoos, conditioners, hair dyes, mousses, foams, gels, creams, lotionsand rinses, all comprising means to semi-permanently and permanentlycolour the hair, and all suitable for use on animals, especially onhumans, and most particularly on the human head.

Compositions which are used to deliver permanent and semi-permanentcolour to the hair, via an oxidative mechanism, are required to be inthe form of a two component composition. One component, which may be ashampoo or conditioner type formulation, carries the dye molecules, andthe other component, which may be described as a developing lotion,carries an oxidising agent, eg hydrogen peroxide.

Prior art compositions used to colour the hair have variousdisadvantages. The new colour fades after, typically, six to eightsubsequent washes of the hair for semi-permanent and twenty totwenty-four washes of the hair for permanents. The regrowth of the hairfrom the roots also reveals the natural colour of the hair, and requiresrecolouring of the hair to avoid this. Thus, to retain the new colourrepeated treatment with hair colouring is required. This is inconvenientand expensive. The ingredients used in many hair colouring compositionsare often noxious and therefore it may also be desirable to reduce thenumber of times hair is exposed to such compositions and/or to reduce orremove the more noxious ingredients from such hair colouringcompositions. Semipermanent and permanent hair colours work by a processof oxidation, and this can lead to oxidation of the hair's lipids andproteins. This is undesirable and can lead to degradation in the hair'scondition.

Therefore it is an object of the present invention to overcome some orall of the aforementioned disadvantages, and in particular to providehair colouring compositions which are gentler and milder to the hair.

According to the invention, there is provided a hair colouringcomposition containing an oxidative hair dye and at least oneantioxidant agent selected from the group consisting of

-   rosmarinus officinalis;-   origanum vulgare;-   camellia sinensis;-   camellia oleifera;-   salvia officinalis;-   apium graveolens;-   thymus vulgaris;-   rosa canina; and-   coriandrum sativum    in combination with a suitable diluent or carrier.

In the process of providing a permanent or semi-permanent colour to thehair, it is required to oxidise the dye molecules so that they reactinto the complex dyestuffs that reside in the hair. Hydrogen peroxide isan example of such an oxidant, and is used to initiate the oxidation ofthe intermediate molecules. Also susceptible to oxidation are the lipidson the surface of the hair and the proteins on and within it. Oxidationof such proteins or the removal of them will lead to a reduction in hairstrength. The oxidation of the hair lipids and proteins can follow achain reaction mechanism, by which hydrogen peroxide is the initiator,and oxidised protein and lipoperoxide are typical products. The hydrogenperoxide molecules degenerate into reactive oxygen species, which arefree radicals, and rapidly start the chain reactions mentionedpreviously.

One way of preventing the oxidative damage would be to use free radicalscavenging agents, eg antioxidants, to mop up the reactive oxygenspecies, preventing the chain reactions. A disadvantage would be thatthe free radical scavengers may also mop up the reactive dyeintermediate once they had been oxidised, and this would prevent dyestuff formation.

To overcome this problem, the present invention is used. The presentinvention relates to the use of anti-oxidants that may be referred to as“chain-breaking”, since they are believed to block the chain reactionsmentioned above from developing far enough to produce lipoperoxide andoxidised proteins on the hair surface and the removal of protein fromthe hair's structure, but do not inhibit the development of colour onthe hair by mopping up the reactive radical dye molecules afteroxidation. Incorporation into the dye formulation or the developinglotion of the product of the “chain-breaking” antioxidants has beenshown to reduce considerably and significantly the levels of lipid andprotein peroxidation on and in the hair surface and during haircolouring with a semi-permanent or permanent hair colouring.

The composition according to the invention may contain a single one ofthe chain-breaking antioxidants. However, the antioxidants have shownsignificant synergistic action in combination with each other, enhancingthe protection of the hair against oxidative damage. This action isshown to be present with no adverse effect on the colour obtained on thehair.

Where the composition contains a single one of the chain-breakingantioxidants, that antioxidant is preferably selected from a preferred,first group of the following antioxidants:

-   origanum vulgare;-   camellia sinensis;-   camellia oleifera;-   apium graveolens; and-   salvia officinalis.

Alternatively, the antioxidant may be one of a second group:

-   rosmarinus officinalis;-   thymus vulgaris;-   rosa canina; and-   coriandrum sativum.

Particularly preferred antioxidants for single use, ie for use incompositions that are free of any of the other antioxidants are:

-   origanum vulgare;-   camellia sinensis-   camellia oleifera; and-   apium graveolens.

Where two of the antioxidants are used in combination, the antioxidantsare preferably one from the first group and one from the second group. Aparticularly preferred antioxidant from the first group is origanumvulgare, which is most preferably used in combination with either rosacanina or thymus vulgaris from the second group.

The composition most preferably comprises three of the antioxidantsnamed above. In such a case, the composition is preferably free of otherantioxidants.

Where three of the antioxidants are used in combination, then theantioxidants most preferably include one or two from the first group andtwo or one respectively from the second group.

It is particularly preferred that the composition should include oneantioxidant from the first group and two from the second group. The twoantioxidants from the second group are preferably selected from rosacanina, coriandrum sativum and thymus vulgaris.

Particularly preferred combinations are combinations of one of

-   camellia oleifera;-   camellia sinensis;-   salvia officinalis; and-   origanum vulgare;    with two of-   rosa canina;-   thymus vulgaris; and-   coriandrum sativum.

Particularly preferred combinations of antioxidants are:

-   camellia oleifera/rosa canina/thymus vulgaris-   camellia sinensis/rosa canina/coriandrum sativum-   salvia officinalis/coriandrum sativum/thymus vulgaris; and-   origanum vulgare/coriandrum sativum/thymus vulgaris.

The first of the above four combinations is especially preferred.

Suitable hairs dyes for use in the hair colouring compositions of thepresent invention include:

-   p-amino phenol, p-phenylenediamine, 4chlororesorcinol, resorcinol,    p-amino-o-cresol, m-aminophenol, p-toluenediamine sulphate,    N,N-bis(hydroxyethyl-p-phenylenediamine) sulphate, 2,5-diamine    toluene sulphate, 4-amino-2-hydroxy toluene, 2-amino    4-hydroxyethylaminoanisole sulphate, o-chloro-p-phenylenediamine    sulphate, 4-nitro-m-phenylenediamine, n-phenyl-p-phenylenediamine,    n-phenyl-p-phenylenediamine sulphate, 1-naphthol,    6-chloro-2-amino4-nitrophenol, 2-amino-3-hydroxy pyridine,    4-amino-3-nitrophenol, 4-amino-m-cresol,    2-methyl-5-hydroxyethylaminophenol, 6-hydroxyindole, 2-methyl    resorcinol, 5-amino-6-chloro-o-cresol,    1-phenyl-3-methyl-5-pyrazolone, 4hydroxypropylamino-2-nitrophenol,    4-hydroxyethlamino-2-nitrophenol, 2,6 diaminopyridine,    m-phenylenediamine, p-aminophenol sulphate, m-aminophenol sulphate,    phenyl methyl pyrazolone, 2,4-diaminophenoxyethanol HCl,    t-butylhydroquinone, p-methyl aminophenol sulphate,    2-amino3-hydroxypyridine, 4-amino-2-hydroxytoluene, p-methyl    aminophenol sulphate, 2,6-dihydroxy-3,4-dimethylpuridine,    1,2-bis-(2,4-diaminophenoxy) propane or 1,5-naphthalenediol.

The particular hair dye and the amount present will depend on thecolorant effect that is desired. The hair dyes may be used incombination to provide the desired shade.

The effectiveness of the antioxidants used in the present invention ininhibiting lipoperoxidation may be demonstrated by the following invitro and ex vivo methods:

In Vitro Method

Hair lipids were extracted, using chloroform/methanol, and then thislipid was subjected to oxidative attack, both with and without thepresence of the antioxidant species. A colourimetric assay was used todetect lipid peroxide with methyl blue, and these levels were quantifiedusing a spectrophotometer.

Ex Vivo Method

Hair swatches were dyed, with and without the presence of theantioxidant species, and then the lipids were extracted from the hairwith chloroform/methanol. Care was taken to ensure that dye moleculeswere not also removed which would then interfere with the assay results.

Methods are as follows:

-   1. Lipid was extracted from the hair.-   2. The supernatant was then dispensed and dried down to leave lipid.-   3. The lipid was then exposed to peroxide solution with and without    antioxidant.-   4. Chloroform/methanol was added. This formed an organic layer    underneath the aqueous peroxide solution. This drew the lipid from    the aqueous solution into the organic layer.-   5. The organic layer was removed and dried down under vacuum.-   6. The lipid was the resuspended in methanol and assayed.

When lipids are extracted from dyed hair, chloroform/methanol is used toextract directly from the hair and the method follows as above.

Where a single antioxidant is present in the composition, the level oflipid peroxidation inhibition is preferably greater than 40%, morepreferably greater than 50%, or greater than 60%.

Where two or three of the antioxidants are present, the inhibition oflipid peroxidation is preferably greater than 60%, and may be greaterthan 70% or greater than 80%.

The hair colouring compositions of the present invention are gentler onthe skin and hair in that they comprise hydrogen peroxide (H₂O₂) and/orammonia (NH₃) in combination with the specified antioxidants, whichreduce the effects of the oxidising agent on the hair and skin.

The antioxidants used in the present invention are plant extracts, whichhave significant flavenoid content:

-   Rosemary—rosmarinus officinalis—(for example the Provital product as    supplied by S Black Ltd, Foxholes Business Park, John Tate Road,    Hertford, Herts, SG13 7YH, United Kingdom),-   Oregano—origanum vulgare—(for),-   Green Tea—camellia sinensis—(for example as supplied by Nichemein    Europe PLC, Am Wehrhan 333, Dusseldorf, Germany),-   Japanese Green Tea—camellia oleifera—(for example as supplied by    Fragrance Oils (International) Ltd, Eton Hill Industrial Estate,    Eton Hill Road, Radcliffe, Manchester, M26 9XT, United Kingdom),-   Sage—salvia officinalis—(for example as supplied by Fragrance Oils    (International) Ltd),-   Celery—apium graveolens—(for example as supplied by Fragrance Oils    (International) Ltd),-   Coriander—coriandrum sativum—(for example as supplied by Fragrance    Oils (International) Ltd),-   Thyme—thymus vulgaris—(for example as supplied by Cosmetochem    International Ltd, Sennweidstrasse 44/46, CH-6312 Steinhausen,/ZG,    Switzerland),-   Rosehip—rosa canina—(for example example the Provital product as    supplied by S Black Ltd).

The results of the in vivo tests described above for the abovechain-breaking antioxidants when used at a level of 0.5% of the totalweight of the composition are given in Table 1: TABLE 1 Inhibition ofLipid Peroxide Antioxidant (0.5% by weight) development Rosemary -rosmarinus officinalis 27% Oregano - origanum vulgare 64% Green Tea -camellia sinensis 51% Japanese Green Tea - camellia 47% oleifera Sage -salvia officinalis 47% Celery - apium graveolens 51% Thyme - thymusvulgaris 26% Rosehips - rosa canina 13% Coriander - coriandrum sativum37%

The total amount of chain-breaking antioxidants used in the haircolouring compositions of the present invention may be in the range of0.1%-5.0% by weight of the total weight of the composition, preferablyin the range of 0.5%-1.5% of the total weight of the composition.

Combinations of two or three of the above show enhanced effects. Theresults of ex vivo tests described above for combinations ofchain-breaking antioxidants are given below in Table 2. In these teststhe a total amount of antoxidant present was 0.5% and equal amounts ofeach antioxidant were used [i.e. if 3 antioxidants were present, eachwas used at 0.167% (0.5%/3)] TABLE 2 Observed inhibition of Expectedlipid peroxide additive Combination of Extracts development effectRosemary + Oregano + Green Tea 70%   46% Rosemary + Oregano + Sage 71%  46% Rosemary + Sage + Celery 71% 41.6% Rosemary + Thyme + Rosehip 72%  22% Thyme + Oregano 70%   45% Thyme + Oregano + Green Tea 76% 45.6%Thyme + Coriander + Sage 78% 36.6% Thyme + Coriander + Oregano 77% 42.3%Rosehip + Oregano 84% 38.5% Rosehip + Coriander + Green Tea 80% 33.6%Rosehip + Japanese Green 72% 28.6% Tea + Thyme

For all the examples given above, the effect observed with a combinationof the antoxidants at a total level of 0.5% is far better than theexpected additive effect. The expected additive effect is calculated asthe sum of inhibition observed (See

Table 1) for each individual antioxidant divided by the number ofantioxidants in combination. For example, for a combination of threeantioxidants the expected additive effect is given by the formulaInhibition of A at 0.5%/3+Inhibition of B at 0.5%/3+Inhibition of C at0.5%/3

Rosemary+Thyme+Rosehip=72% reduction in lipid peroxidation. This isgreater than the additive effect, which is 22% reduction, so shows asynergistic effect. Expected additivereduction=(27/3)+(26/3)+(13/3)=22%.

-   Rosehip+Oregano=84% reduction in lipid peroxidation. This is greater    than the additive effect, which is 38.5% reduction, so shows a    synergistic effect. Expected additive reduction=(13/2)+(64/2)=38.5%.

Similarly for the other combinations, the observed effects are greaterthan the expected additive effect showing that the combinations aresynergistic.

Certain antioxidants did not work, and actually induced more lipidperoxidation. This effect was also enhanced when these were incombination.

An example is Eucalyptus (+50%)+Passionflower (+116.5%)+Yarrow(+81.8%)=+202% more lipid peroxidation to the hair. Showing that thesynergistic effects can also be replicated with the compounds thatinduced damage to the hair.

The present invention can be delivered to hair via any of theconventional formulation known to those skilled in the art, such asshampoos, conditioners (both emulsion and non-emulsion types), lotions(including developing lotions), sprays, gels, waxes, serums, mousses,tonics etc. Of these types of formulation, the range of ingredients canbe broad. Such ingredients are surfactants, conditioning agents, waxes,thickeners, preservatives, and resins, sequestering agents, slip aids,vitamins, gelling agents, pearlising agents, pH adjusting agents andsunscreening agents.

The composition may include a surfactant such as cosmetically acceptablesalts of alkyl ether sulphates (such as ammonium laureth sulphate orsodium laureth sulphate), alkyl and alkylamidoalkyl betaines (such ascocamidopropyl betaine), ethoxylated alcohols, polyethyleneglycolcarboxylates, accepted salts of alkyl sulphates (such as ammonium laurylsulphate or sodium lauryl sulphate), sulphosuccinates (such as disodiumlaureth sulphosuccinate), amphoacetates and amphodiacetates (such asdisodium cocoamphodiacetates), alkylglucosides and alcohol sulphonates,incorporated in an amount of from about 1% to 99% by weight of thecomposition.

The composition may also include a thickener or viscosity controllingagent such as an amine oxide, block polymers of ethylene oxide andpropylene oxide (for examples, those available from BASF Wyandotte underthe trade name “Pluronic” RTM), ethoxylated fatty alcohols, cellulosicderivatives (such as hydroxypropylmethyl cellulose), salt (NaCl),phthalic acid amide, polyvinylalcohols and fatty alcohols, suitably inan amount from about 0.5% to about 10% by weight of the compostion.

Sequestering agents may be added to the composition, such asethylenediamine tetraacetic acid (EDTA) and salts thereof, suitably inan amount of from about 0.005% to about 0.5% by weight of thecomposition.

Also included in the composition may be waxes such as cocoa butter,suitably in an amount of from about 0.01% to about 1.0% by weight of thecomposition. The composition may also include gelling agents such asPVM, MA or a decadiene crosspolymer (available under the trade nameStabilez 06), suitably in an amount from about 0.1% to 2.0% by weight ofthe composition.

Pearlising agents may be included eg stearic monoethanolamine, suitablyin an amount from about 0.01% to about 10% by weight of the composition.The pH of the composition is generally required to be in the range of 8to 12, preferably in the range of 9-10.5, for the desired performance asa permanent hair colour. To achieve this, the composition may need to bebuffered using means well known in the art, such as a system comprisingsuccinic acid, citric acid, lactic acid and acceptable salts thereof,phosphoric acid, mono or disodium phosphate and sodium carbonate. The pHmay be adjusted with an agent such as sodium hydroxide, aminomethylpropanol, triethanolamine and caustic potash, suitably in an amount fromabout 0.01% to about 10% by weight of the composition.

If the composition is in the form of an emulsion, the emulsifiers usedmay be any emulsifiers known in the art for use in water-in-oil oroil-in-water emulsions, examples of which follow:

-   a) sesquioleates such as sorbitan sesquioleate, available    commercially for example under the trade name Arlacel 83 (ICI), or    polyglyceryl-2-sesquioleate;-   b) ethoxylated esters of derivatives of natural oils such as the    polyethoxylated ester of hydrogenated castor oil available    commercially for example under the trade name Arlacel 989 (ICI);-   c) silicone emulsifiers such as silicone polyols available    commercially for example under the trade name ABIL WS08 (Th.    Goldschmidt AG);-   d) anionic emulsifiers such as fatty acid soaps eg potassium    stearate and fatty acid sulphates eg sodium cetostearyl sulphate    available commercially under the trade name Dehydag (Henkel);-   e) ethoxylated fatty alcohols, for example the emulsifiers available    commercially under the trade name Brij (ICI);-   f) sorbitan esters, for example the emulsifiers available    commercially under the trade name Span (ICI);-   g) ethoxylated sorbitan esters, for example the emulsifiers    available commercially under the trade name Tween (ICI);-   h) ethoxylated fatty acid esters such as ethoxylated stearates, for    example the emulsifiers available commercially under the trade name    Myrj (ICI);-   i) ethoxylated mono-, di-, and tri-glycerides, for example the    emulsifiers available commercially under the trade name Labrafil    (Alfa Chem.);-   j) non-ionic self-emulsifying waxes, for example the wax available    commercially under the trade name Polawax(Croda);-   k) ethoxylated fatty acids, for example the emulsifiers available    commercially under the trade name Tefose (Alfa Chem.); or-   l) mixtures thereof.

The amount of emulsifier present in the water-in-oil compositions of thepresent disclosure is preferably in the range 0.1 to 10%.

The invention will be illustrated by the following Examples, which aregiven by way of example only. The “Antioxidant” in these Examples may beany one of the antioxidants referred to above or a combination of two orthree of these antioxidants, eg the preferred combinations set outabove. The type and amount of hair dye to be incorporated will depend onthe colorant effect desired.

EXAMPLE 1 Surfactant (Shampoo) Base Component Carrying the Hair DyeMolecules

% w/w 1. Cocamide MEA 3.5 2. Glycol Distrearate 3.5 3. Sodium Gluceptate0.25 4. Sodium Metabisulfate 2.0 5. Sodium Erthroborate 0.3 6.Cocamidopropyl Betaine 6.625 7. Dilute Sodium Lauryl-ether Sulfate 25.758. Laureth-3 10 9. Oleic acid 4 10. Ammonia 3.5 11. Citric acidmonohydrate 0.1 12. Hair Dyes qs 13. Antioxidant 0.5% 14. Purified waterto 100%Method

-   1. Heat 1, 2 & 8 to 70-75° C., until melted.-   2. Disperse 3, 4, 5, 11 & 12 into 14 and heat to 70-75° C.-   3. Stir in 6 & 7, to water phase, and maintain at 70-75° C.-   4. Add oils phase to water phase and homogenise for 10 minutes.-   5. Cool to <35° C.-   6. Stir in 9 & 10 slowly, followed by 13.

EXAMPLE 2 Emulsion (Conditioner) Base Component Carrying the Hair DyeMolecules

% w/w 1. Tetra sodium EDTA 0.14 2. Sodium Benzoate 0.1 3. Phenoxyethanol0.1 4. Citric asid monohydrate 1.5 5. Ceteath-25 1.5 6. Cetearyl alcohol2.25 7. Stearyl alcohol 2.25 8. Hair dyes qs 9. Antioxidant 0.5% 10.Purified water to 100%Method

-   1. Heat 5, 6 & 7 to 70-75° C.-   2. Disperse 1, 2, 4 & 8 into 10. Heat t o70-75° C.-   3. Add oils to water phase and homogenise for 10 minutes.-   4. Cool to <35° C.-   5. Stir in 3, followed by 9.

EXAMPLE 3 Developing Lotion Component Carrying the Oxidising Agent

% w/w 1. Tetra sodium EDTA 0.1 2. Phosphoric acid 0.1 3. Hydrogenperoxide solution (65%) 25.0 4. Ceteath-20 2.0 5. Cetearyl alcohol 4.06. Sodium Stannate 0.005 7. Antioxidant 0.5% 8. Purified water to 100%Method

-   1. Disperse 1, 2 & 6 into 8. Heat to 70-75° C.-   2. Heat 4 & 5 to 70-75° C. until melted.-   3. Add oils to water and homogenise for 10 minutes.-   4. Cool to <35° C.-   5. Stir in 3, followed by 7.

In use, a conventional product combination would be the shampoo orconditioner base product (for example the formulation of Example 1 orExample 2) carrying the hair dye molecules and the developing lotion(for example the formulation of Example 3) that delivers the oxidisingagent, which in the case of Example 3 is hydrogen peroxide, but could beanother oxidising agent. Typically, equal volumes of the baseformulation and the developing lotion are mixed together, to oxidativelyactivate the dye molecule to react with each other. This mixture is thenapplied to dry hair for any time from about 10 minutes to about 60minutes. The hair is then rinsed with water and usually a shampoo orconditioner is used. This is followed by drying of the hair, naturallyor by towel, or the use of a hair dryer. The chain-breaking antioxidantagents of the present invention can be included in either the baseformulation, which carries the dyes (such as a shampoo-type formula, ora conditioner emulsion-type formula). Other types of carrier of the dyemolecules and the chain-breaking antioxidants may be used such asmousses, foams, gels, creams, lotions and rinses, which may or may notbe used in conjunction with a second component.

1-24. Cancel
 25. A hair colouring composition containing an oxidativehair dye and two or more antioxidant agents selected from the groupconsisting of rosmarinus officinalis; origanum vulgare; camelliasinensis; camellia oleifera; salvia officinalis; apium graveolen; thymusvulgaris; rosa canina; and coriandrum sativum in combination with asuitable diluent or carrier.
 26. Hair colouring composition as claimedin claim 25, which includes two of said antioxidants, including oneantioxidant selected from a first group consisting of origanum vulgare;camellia sinensis; camellia oleifera; apium graveolens; and salviaofficinalis and the other of said antioxidants is selected from a secondgroup consisting of rosmarinus officinalis; thymus vulgaris; rosacanina; and coriandrum sativum.
 27. Hair colouring composition asclaimed in claim 25, wherein the antioxidant from the first group isoriganum vulgare.
 28. Hair colouring composition as claimed in claim 27,wherein the antioxidant from the second group is either rosa canina orthymus vulgaris.
 29. Hair colouring composition as claimed in claim 25,which comprises three of said antioxidants.
 30. Hair colouringcomposition as claimed in claim 26, wherein one or two of saidantioxidants are selected from the first group defined in claim 26 andtwo or one respectively are selected from the second group defined inclaim
 26. 31. Hair colouring composition as claimed in claim 30,comprising one antioxidant from the first group and two from the secondgroup.
 32. Hair colouring composition as claimed in claim 31, whereinthe two antioxidants from the second group are selected from rosacanina, coriandrum sativum and thymus vulgaris.
 33. Hair colouringcomposition as claimed in claim 32, wherein the antioxidant from thefirst group is selected from the group consisting of camellia oleifera;camellia sinensis; salvia officinalis; and origanum vulgare.
 34. Haircolouring composition as claimed in claim 33, wherein the compositioncomprises one of the following combinations of antioxidants: camelliaoleifera/rosa canina/thymus vulgaris camellia sinensis/rosacanina/coriandrum sativum salvia officinalis/coriandrum sativum/thymusvulgaris; and origanum vulgare/coriandrum sativum/thymus vulgaris. 35.Hair colouring composition as claimed in claim 34, wherein thecombination of antioxidants is camellia oleifera/rosa canina/thymusvulgaris.
 36. Hair colouring composition as claimed in claim 25, whereinthe total amount of antioxidant agents lies in the range of 0.1% to 5.0%of the total weight of the composition.
 37. Hair colouring compositionas claimed in claim 25, wherein the total amount of antioxidant agentspresent lies in the range of 0.5%-1.5% of the total composition byweight.
 38. Hair colouring composition as claimed in claim 25, whichexhibits a level of lipid peroxidation inhibition of greater than 60%.39. Hair colouring composition as claimed in claim 25, wherein the hairdye is selected from the group consisting of p-amino phenol,p-phenylenediamine, 4-chlororesorcinol, resorcinol, p-amino-o-cresol,m-aminophenol, p-toluenediamine sulphate,N,N-bis(hydroxyethyl-p-phenylenediamine) sulphate, 2,5-diamine toluenesulphate, 4-amino-2-hydroxy toluene, 2-amino 4-hydroxyethylaminoanisolesulphate, o-chloro-p-phenylenediamine sulphate,4-nitro-m-phenylenediamine, n-phenyl-p-phenylenediamine,n-phenyl-p-phenylenediamine sulphate, 1-naphthol,6-chloro-2-amino-4-nitrophenol, 2-amino-3-hydroxy pyridine,4-amino-3-nitrophenol, 4-amino-m-cresol,2-methyl-5-hydroxyethylaminophenol, 6-hydroxyindole, 2-methylresorcinol, 5-amino-6-chloro-o-cresol, 1-phenyl-3-methyl-5-pyrazolone,4-hydroxypropylamino-2-nitrophenol, 4-hydroxyethlamino-2-nitrophenol,2,6 diaminopyridine, m-phenylenediamine, p-aminophenol sulphate,m-aminophenol sulphate, phenyl methyl pyrazolone,2,4-diaminophenoxyethanol HCl, t-butylhydroquinone, p-methyl aminophenolsulphate, 2-amino3-hydroxypyridine, 4-amino-2-hydroxytoluene, p-methylaminophenol sulphate, 2,6-dihydroxy-3,4-dimethylpuridine, and1,2-bis-(2,4-diaminophenoxy) propane or 1,5-naphthalenediol.
 40. Haircolouring composition as claimed in claim 25, in the form of aformulation selected from the group consisting of shampoos,conditioners, lotions, sprays, gels, waxes, serums, mousses, and tonics.41. Hair colouring composition as claimed in claim 40, furthercomprising one or more excipients selected from surfactants,conditioning agents, waxes, thickeners, preservatives, resins,sequestering agents, slip aids, vitamins, gelling agents, pearlisingagents, pH adjusting agents and sunscreening agents.
 42. Hair colouringcomposition as claimed in claim 25, which is in the form of atwo-component formulation, a first component including one or more hairdyes and a second component including an oxidising agent.
 43. Haircolouring composition as claimed in claim 25, which comprises hydrogenperoxide as oxidising agent.
 44. A method of permanently orsemi-permanently colouring hair by means of an oxidative process, whichmethod comprises application to the hair of a hair colouring compositionas claimed in claim 25.